EP2902533A1 - Silberplattierungsmaterial und verfahren zur herstellung davon - Google Patents

Silberplattierungsmaterial und verfahren zur herstellung davon Download PDF

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Publication number
EP2902533A1
EP2902533A1 EP13842760.4A EP13842760A EP2902533A1 EP 2902533 A1 EP2902533 A1 EP 2902533A1 EP 13842760 A EP13842760 A EP 13842760A EP 2902533 A1 EP2902533 A1 EP 2902533A1
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EP
European Patent Office
Prior art keywords
silver
plated product
base material
plated
heat
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EP13842760.4A
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English (en)
French (fr)
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EP2902533A4 (de
Inventor
Keisuke Shinohara
Masafumi Ogata
Hiroshi Miyazawa
Akira Sugawara
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Dowa Metaltech Co Ltd
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Dowa Metaltech Co Ltd
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Publication of EP2902533A1 publication Critical patent/EP2902533A1/de
Publication of EP2902533A4 publication Critical patent/EP2902533A4/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/041—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/025—Composite material having copper as the basic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/041—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
    • H01H11/045—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion with the help of an intermediate layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/041—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
    • H01H2011/046—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion by plating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R2201/00—Connectors or connections adapted for particular applications
    • H01R2201/26—Connectors or connections adapted for particular applications for vehicles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12896—Ag-base component

Definitions

  • the present invention generally relates to a silver-plated product and a method for producing the same. More specifically, the invention relates to a silver-plated product used as the material of contact and terminal parts, such as connectors, switches and relays, which are used for on-vehicle and/or household electric wiring, and a method for producing the same.
  • plated products wherein a base material of stainless steel, copper, a copper alloy or the like, which is relatively inexpensive and which has excellent corrosion resistance, mechanical characteristics and so forth, is plated with tin, silver, gold or the like in accordance with required characteristics, such as electrical and soldering characteristics.
  • Tin-plated products obtained by plating a base material of stainless steel, copper, a copper alloy or the like, with tin are inexpensive, but they do not have good corrosion resistance in a high-temperature environment.
  • Gold-plated products obtained by plating such a base material with gold have excellent corrosion resistance and high reliability, but the costs thereof are high.
  • silver-plated products obtained by plating such a base material with silver are inexpensive in comparison with gold-plated products and have excellent corrosion resistance in comparison with tin-plated products.
  • a metal plate for electrical contacts As a silver-plated product obtained by plating a base material of stainless steel, copper, a copper alloy or the like with silver, there is proposed a metal plate for electrical contacts, wherein a silver plating layer having a thickness of 1 micrometer is formed on a copper plating layer having a thickness of 0.1 to 0.5 ⁇ m which is formed on a nickel plating layer having a thickness of 0.1 to 0.3 ⁇ m which is formed on the surface of a thin base material plate of stainless steel (see, e.g., Japanese Patent No. 3889718 ).
  • a silver-coated stainless bar for movable contacts wherein a surface layer of silver or a silver alloy having a thickness of 0.5 to 2.0 ⁇ m is formed on an intermediate layer of at least one of nickel, a nickel alloy, copper and a copper alloy having a thickness of 0.05 to 0.2 ⁇ m, the intermediate layer being formed on an activated underlying layer of nickel which has a thickness of 0.01 to 0.1 ⁇ m and which is formed on a base material of stainless steel (see, e.g., Japanese Patent No. 4279285 ).
  • a silver-coated material for movable contact parts wherein a surface layer of silver or a silver alloy having a thickness of 0.2 to 1.5 ⁇ m is formed on an intermediate layer of copper or a copper alloy having a thickness of 0.01 to 0.2 ⁇ m, the intermediate layer being formed on an underlying layer of any one of nickel, a nickel alloy, cobalt or a cobalt alloy which has a thickness of 0.005 to 0.1 ⁇ m and which is formed on a metallic substrate of copper, a copper alloy, iron or an iron alloy, the arithmetic average roughness Ra of the metallic substrate being 0.001 to 0.2 ⁇ m, and the arithmetic average roughness Ra after forming the intermediate layer being 0.001 to 0.1 ⁇ m (see, e.g., Japanese patent Laid-Open No. 2010-146925 ).
  • the arithmetic average roughness Ra of a pressure roll is adjusted to be 0.001 to 0.2 ⁇ m so that the arithmetic average roughness Ra of a metallic substrate, which is transferred by the pressure roll, is adjusted to be 0.001 to 0.2 ⁇ m. It is also required to appropriately choose the current density in plating and the kinds of additives in a plating solution during the formation of the intermediate layer to adjust the arithmetic average roughness Ra to be 0.001 to 0.1 ⁇ m after forming the intermediate layer, so that the process is complicated and the costs thereof are increased.
  • the applicant has proposed to produce an inexpensive silver-plated product, which has good adhesion properties of the plating film and which can restrain the rise of the contact resistance of the product even if it is used in a high-temperature environment, by causing the crystalline diameter in a direction perpendicular to ⁇ 111 ⁇ plane of the surface layer to be 300 angstroms or more in a silver-plated product wherein a surface layer of Ag is formed on an intermediate layer of Cu which is formed on an underlying layer of Ni formed on the surface of a base material of stainless steel (Japanese Patent Application No. 2010-253045 ).
  • the inventors have diligently studied and found that it is possible to produce a silver-plated product, which has a good bendability and which can restrain the rise of the contact resistance thereof even if it is used in a high-temperature environment, if the area fraction in ⁇ 200 ⁇ orientation of a surface layer of silver is 15 % or more in a silver-plated product wherein the surface layer is formed on the surface of a base material or on the surface of an underlying layer formed on the base material.
  • the inventors have made the present invention.
  • a silver-plated product comprising: a base material; and a surface layer of silver which is formed on a surface of the base material or on a surface of an underlying layer formed on the base material, wherein an area fraction in ⁇ 200 ⁇ orientation of the surface layer is 15 % or more.
  • the surface layer is preferably formed on the surface of the base material of copper or a copper alloy, or on the surface of the underlying layer of copper or a copper alloy formed on the base material.
  • a method for producing a silver-plated product comprising the steps of: preparing a base material; forming a surface layer of silver on a surface of the base material or on a surface of an underlying layer formed on the base material; and thereafter, carrying out an aging treatment, wherein the surface layer is formed by electroplating in a silver plating bath which contains 1 to 15 mg/L of selenium and wherein a mass ratio of silver to free cyanogen is in the range of from 0.9 to 1.8.
  • the aging treatment is preferably carried out by holding at a temperature of 10 to 100 °C for 1 hours or more.
  • the surface layer is preferably formed on the surface of the base material of copper or a copper alloy, or on the surface of the underlying layer of copper or a copper alloy formed on the base material.
  • a contact or terminal part which is made of the above-described silver-plated product.
  • area fraction in ⁇ 200 ⁇ orientation means a percentage (%) of an area occupied by crystals having ⁇ 200 ⁇ orientation directed to a normal direction (ND) to the surface of a silver-plated product (with a permissible deviation in angle of 10° or less), with respect to the area of the surface of the silver-plated product.
  • the present invention it is possible to produce a silver-plated product, which has a good bendability and which can restrain the rise of the contact resistance thereof even if it is used in a high-temperature environment.
  • a surface layer of silver is formed on the surface of a base material or on the surface of an underlying layer formed on the base material, and the area fraction in ⁇ 200 ⁇ orientation of the surface layer of silver is 15 % or more, preferably 20 % or more, and more preferably 25 % or more. Furthermore, if the area fraction in ⁇ 200 ⁇ orientation of the surface layer of the silver-plated product is higher, it is possible to further improve the bendability of the silver-plated product and to further restrain the rise of the contact resistance thereof even if it is used in a high-temperature environment.
  • the surface layer of silver is preferably formed on the surface of the base material of copper or a copper alloy, or on the surface of the underlying layer of copper or a copper alloy formed on the base material.
  • the surface layer of the silver-plated product contains silver, and may be made of a silver alloy if the area fraction in ⁇ 200 ⁇ orientation of the surface layer is 15 % or more.
  • the thickness of the surface layer of silver is preferably in the range of from 0.5 ⁇ m to 20 ⁇ m.
  • the surface layer is formed by electroplating in a silver plating bath which contains 1 to 15 mg/L of selenium and wherein a mass ratio of silver to free cyanogen is in the range of from 0.9 to 1.8, and thereafter, an aging treatment is carried out. If the content of selenium in the silver plating bath and/or the mass ratio of silver to free cyanogen are beyond the above limits, it is not possible to increase the area fraction in ⁇ 200 ⁇ orientation of the surface layer of the silver-plated product.
  • the aging treatment is preferably carried out by holding at a temperature of 10 to 100 °C for 1 hour or more.
  • This aging treatment may be carried out by means of a temperature and humidity testing chamber or the like in order to hold aging conditions, or may be carried out by allowing to stand in an open system (open space) if conditions are satisfied.
  • the surface layer of silver is preferably formed on the surface of the base material of copper or a copper alloy, or on the surface of the underlying layer of copper or a copper alloy formed on the base material.
  • the temperature of the solution is preferably 10 to 40 °C, more preferably 15 to 30 °C, and the current density is preferably 1 to 15 A/dm 2 , more preferably 3 to 10 A/dm 2 .
  • the silver plating bath is preferably a silver plating bath which comprises silver potassium cyanide (KAg(CN) 2 ), potassium cyanide (KCN), and 2 to 30 mg/L of potassium selenocyanate (KSeCN) and wherein the concentration of selenium in the silver plating bath is 1 to 15 mg/L, the mass ratio of silver to free cyanogen being in the range of from 0.9 to 1.8.
  • KAg(CN) 2 silver potassium cyanide
  • KCN potassium cyanide
  • KSeCN potassium selenocyanate
  • an electrolytic degreasing or dipping degreasing is preferably carried out for removing adhesion substances and so forth from the base material (a material to be plated), and pickling is preferably carried out for removing oxides and so forth from the base material.
  • pickling is preferably carried out for removing oxides and so forth from the base material.
  • a pure copper plate having a size of 67 mm x 50 mm x 0.3 mm was prepared as a base material (a material to be plated).
  • the material to be plated and a SUS plate were put in an alkali degreasing solution to be used as a cathode and an anode, respectively, to carry out electrolytic degreasing at 5 V for 30 seconds.
  • the material thus electrolytic-degreased was washed, and then, pickled for 15 seconds in a 3% sulfuric acid.
  • the material to be plated and a titanium electrode plate coated with platinum were used as a cathode and an anode, respectively, to electroplate (silver-strike-plate) the material at a current density of 2.5 A/dm 2 for 10 seconds in a silver strike plating bath comprising 3 g/L of silver potassium cyanide and 90 g/L of potassium cyanide while stirring the solution at 400 rpm by a stirrer.
  • the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 74 g/L of silver potassium cyanide (KAg(CN) 2 ), 100 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate (KSeCN), while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 40 g/L, the concentration of free CN being 40 g/L, and the mass ratio of Ag to free CN being 1.00.
  • a silver plating bath comprising 74 g/L of silver potassium cyanide (KAg(CN) 2 ), 100 g/L of potassium
  • the area fraction in ⁇ 200 ⁇ orientation of the silver-plated product was obtained by calculating a proportion occupied by crystals having ⁇ 200 ⁇ orientation directed to a normal direction (ND) to the surface of the silver-plated product (with a permissible deviation in angle of 10° or less), by the electron backscatter diffraction (EBSD) using a crystal analysis tool for scanning electron microscope (OIM produced by TSL solutions Co., Ltd.), after measuring a square of 100 ⁇ m x 100 ⁇ m on the surface of the silver-plated product at a step of 0.4 ⁇ m by means of a thermal field emission-type scanning electron microscope (JSM-7800F produced by JEOL Ltd.). As a result, the area fraction in ⁇ 200 ⁇ orientation was 36.7 %.
  • the theoretical value of the area fraction in ⁇ 200 ⁇ orientation of a silver-plated product having non-orientation is about 4.6 %.
  • most of crystals in the silver plating film of the surface layer of the silver-plated product in this example are strongly oriented so that ⁇ 200 ⁇ plane is directed to the surface (plate surface) of the silver-plated product ( ⁇ 200 ⁇ orientation is directed to the normal direction (ND) to the surface of the silver-plated product).
  • the heat resisting property of the silver-plated product was evaluated by measuring a contact resistance thereof at a load of 50 gf by means of an electrical contact simulator (CRS-1 produced by Yamasaki-Seiki Co., Ltd.) before and after a heat-proof test in which the silver-plated product was heated at 200 °C. for 144 hours by means of a dryer (OF450 produced by AS ONE Corporation).
  • the contact resistance of the silver-plated product was 0.9 m ⁇ before the heat-proof test and 2.3 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • JIS Japanese Industrial Standard
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 111 g/L of silver potassium cyanide, 100 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 60 g/L, the concentration of free CN being 40 g/L, and the mass ratio of Ag to free CN being 1.51.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 41.9 %.
  • the contact resistance of the silver-plated product was 0.8 m ⁇ before the heat-proof test and 2.5 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 111 g/L of silver potassium cyanide, 120 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 60 g/L, the concentration of free CN being 48 g/L, and the mass ratio of Ag to free CN being 1.26.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 43.2 %.
  • the contact resistance of the silver-plated product was 0.9 m ⁇ before the heat-proof test and 2.5 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 111 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 60 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.08.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 37.9 %.
  • the contact resistance of the silver-plated product was 0.8 m ⁇ before the heat-proof test and 3.2 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 120 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 48 g/L, and the mass ratio of Ag to free CN being 1.67.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 45.9 %.
  • the contact resistance of the silver-plated product was 0.7 m ⁇ before the heat-proof test and 2.0 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 41.6 %.
  • the contact resistance of the silver-plated product was 0.9 m ⁇ before the heat-proof test and 2.4 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 11 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 6 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 44.4 %.
  • the contact resistance of the silver-plated product was 1.0 m ⁇ before the heat-proof test and 2.4 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 26 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 14 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 42.2 %.
  • the contact resistance of the silver-plated product was 0.8 m ⁇ before the heat-proof test and 3.6 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 2 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 1 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 27.8 %.
  • the contact resistance of the silver-plated product was 1.0 m ⁇ before the heat-proof test and 3.9 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 6 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 1 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 41.7 %.
  • the contact resistance of the silver-plated product was 1.0 m ⁇ before the heat-proof test and 1.9 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was a good value which was not higher than 5 m ⁇ , so that the rise of the contact resistance was restrained after the heat-proof test.
  • the exposure of the base material was not observed in the silver-plated product after bending, so that the bendability of the silver-plated product was good.
  • a silver-plated product was produced by the same method as that in Example 6, except that an aging treatment was carried out at a temperature of 50 °C using a temperature and humidity testing chamber (Low-temperature quartz temperature and humidity testing chamber ⁇ -201R produced by Isuzu Seisakusho Co. Ltd.).
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 36.1 %.
  • a silver-plated product was produced by the same method as that in Example 11, except that the aging temperature was 100 °C.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 31.5 %.
  • a silver-plated product was produced by the same method as that in Example 8, except that an aging treatment was carried out at a temperature of 50 °C using the same temperature and humidity testing chamber as that in Example 11.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 39.2 %.
  • a silver-plated product was produced by the same method as that in Example 6, except that electroplating (silver plating) was carried out until a silver plating film having a thickness of 1 ⁇ m was formed.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 32.8 %.
  • a silver-plated product was produced by the same method as that in Example 6, except that electroplating (silver plating) was carried out until a silver plating film having a thickness of 5 ⁇ m was formed.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 56.5 %.
  • a silver-plated product was produced by the same method as that in Example 6, except that electroplating (silver plating) was carried out until a silver plating film having a thickness of 20 ⁇ m was formed.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1. As a result, the area fraction in ⁇ 200 ⁇ orientation was 66.7 %.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 74 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 40 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 0.72.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 8.9 %.
  • the contact resistance of the silver-plated product was 0.8 m ⁇ before the heat-proof test and 5.6 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 100 g/L of potassium cyanide and 18 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 10 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 40 g/L, and the mass ratio of Ag to free CN being 2.01.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 5.5 %.
  • the contact resistance of the silver-plated product was 0.9 m ⁇ before the heat-proof test and 12.3 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 36 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 20 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 4.6 %.
  • the contact resistance of the silver-plated product was 0.9 m ⁇ before the heat-proof test and 15.7 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 55 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 30 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 3.9 %.
  • the contact resistance of the silver-plated product was 0.7 m ⁇ before the heat-proof test and 94.2 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 73 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 40 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 4.0 %.
  • the contact resistance of the silver-plated product was 0.7 m ⁇ before the heat-proof test and 574.5 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • a silver-plated product was produced by the same method as that in Example 1, except that the material to be plated and a silver electrode plate were used as a cathode and an anode, respectively, to electroplate (silver-plate) the material at a current density of 5 A/dm 2 and a liquid temperature of 18 °C in a silver plating bath comprising 148 g/L of silver potassium cyanide, 140 g/L of potassium cyanide and 1 mg/L of potassium selenocyanate, while stirring the solution at 400 rpm by a stirrer, until a silver plating film having a thickness of 3 ⁇ m was formed. Furthermore, in the used silver plating bath, the concentration of Se was 0.5 mg/L, and the concentration of Ag was 80 g/L, the concentration of free CN being 56 g/L, and the mass ratio of Ag to free CN being 1.44.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated by the same method as that in Example 1, and the contact resistances thereof before and after the heat-proof test and the bendability thereof were evaluated by the same methods as those in Example 1.
  • the area fraction in ⁇ 200 ⁇ orientation was 10.4 %.
  • the contact resistance of the silver-plated product was 1.0 m ⁇ before the heat-proof test and 6.5 m ⁇ after the heat-proof test.
  • the contact resistance after the heat-proof test was not a good value which was not higher than 5 m ⁇ , so that the contact resistance was raised after the heat-proof test.
  • cracks were observed in the silver-plated product after bending, and the base material was exposed, so that the bendability of the silver-plated product was not good.
  • Table 1 Composition of Silver Plating Bath Silver Plating Bath KAg(CN) 2 (g/L) KCN (g/L) KSeCN (mg/L) Se (mg/L) Ag (g/L) Free CN (g/L) Ag/ Free CN Ex.1 74 100 18 10 40 40 1.00 Ex.2 111 100 18 10 60 40 1.51 Ex.3 111 120 18 10 60 48 1.26 Ex.4 111 140 18 10 60 56 1.08 Ex.5 148 120 18 10 80 48 1.67 Ex.6 148 140 18 10 80 56 1.44 Ex.7 148 140 11 6 80 56 1.44 Ex.8 148 140 26 14 80 56 1.44 Ex.9 148 140 2 1 80 56 1.44 Ex.10 148 140 6 3 80 56 1.44 Ex.11 148 140 18 10 80 56 1.44 Ex.12 148 140 18 10 80 56 1.44 Ex.13 148 140
  • the intensities (10000 cps) at the X-ray diffraction (XRD) peak on each of ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ planes of the silver plating film were obtained when the aging time was 1, 3, 7, 24, 72 and 168 hours, respectively, and the full-width at half maximum of a diffraction intensity curve at the XRD peak on ⁇ 111 ⁇ plane was obtained.
  • an X-ray diffraction (XRD) analyzer (a full-automatic multi-purpose horizontal X-ray diffractometer Smart Lab produced by Rigaku Corporation) was used for obtaining each of the intensities at the X-ray diffraction (XRD) peak by scanning in a scanning range of 2 ⁇ / ⁇ using an X-ray tube of Cu and a K ⁇ filter after 1, 3, 7, 24, 72 and 168 hours, respectively, immediately from the silver plating, while holding the silver-plated product at a temperature of 25 °C and a relative humidity of 50 %RH.
  • XRD X-ray diffraction
  • the intensity at the X-ray diffraction (XRD) peak on ⁇ 200 ⁇ plane and the full-width at half maximum of the diffraction intensity curve at the XRD peak on ⁇ 111 ⁇ plane were hardly changed by the aging treatment, whereas in the case of the silver-plated product in Example 7 as shown in FIG. 5 , the intensity at the X-ray diffraction (XRD) peak on ⁇ 200 ⁇ plane was remarkably increased by the aging treatment, and the full-width at half maximum of the diffraction intensity curve at the XRD peak on ⁇ 111 ⁇ plane was remarkably decreased by the aging treatment.
  • the area fraction in ⁇ 200 ⁇ orientation was in the range of from 4.1 % to 4.6 %.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was calculated. As a result, it was 4.6 %.
  • the area fraction in ⁇ 200 ⁇ orientation of each of the silver-plated products in Examples 1 to 16 was in the range of from 27.8 % to 66.7 %.
  • the area fraction in ⁇ 200 ⁇ orientation thereof was very high (above ten times) as compared with those of the commercially available silver-plate product and the imaginary silver-plated product estimated so as to be oriented at random. This shows that most of crystals in the silver plating film of the surface layer of the silver-plated product in each of Examples 1 through 16 are strongly oriented so that ⁇ 200 ⁇ plane is directed to the surface (plate surface) of the silver-plated product. Furthermore, although it is known that a copper alloy plate having a high area fraction in ⁇ 200 ⁇ orientation and a high twin crystal density has an excellent bendability, it was found that a silver-plated product having a high area fraction in ⁇ 200 ⁇ orientation as that in Examples 1 through 16 has an excellent bendability.
  • the intensities (10000 cps) at the X-ray diffraction (XRD) peak on each of ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ planes of the silver plating film were obtained when the silver-plated products were held at 200 °C for 0.5, 1, 3 and 24 hours, respectively.
  • an X-ray diffraction (XRD) analyzer (a full-automatic multi-purpose horizontal X-ray diffractometer Smart Lab produced by Rigaku Corporation) was used for obtaining each of the intensities at the X-ray diffraction (XRD) peak by scanning in a scanning range of 2 ⁇ / ⁇ using an X-ray tube of Cu and a K ⁇ filter after 0.5, 1, 3 and 24 hours, respectively, immediately from the silver plating, while holding the silver-plated products at a temperature of 200 °C.
  • XRD X-ray diffraction
  • the intensities at the X-ray diffraction (XRD) peak on each of ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ planes were remarkably increased when it was held at a high temperature (200 °C), whereas in the silver-plated product in Example 6 as shown in FIG. 7 , the intensities at the X-ray diffraction (XRD) peak on each of ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ planes were hardly changed even if it was held at a high temperature (200 °C).
  • FIGS. 8 and 9 show a backscattered electron image of a cross-section of the silver plating film of each of the silver-plated products in Example 6 and Comparative Example 4, the image being obtained by a thermal field emission-type scanning electron microscope (JSM-7800F produced by JEOL Ltd.).
  • JSM-7800F thermal field emission-type scanning electron microscope
  • a female terminal 11 and a male terminal 12 (or a portion of one contacting the other) of a connecting terminal comprising the female terminal 11 and the male terminal 12 fitted into the female terminal 11 is made of a silver-plated product according to the present invention, it is possible to produce a connecting terminal wherein it is difficult to form cracks by bending during press working and which can restrain the rise of the contact resistance thereof when it is used in a high temperature environment. Therefore, the silver-plated product can be used as the material of charge terminals and high-pressure connectors of electric vehicles (EVs) and hybrid electric vehicles (HEVs), in which heavy-current flow and which have large heating values.
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • a silver-plated product according to the present invention can be used as the material of contact and terminal parts, such as connectors, switches and relays, which are used for on-vehicle and/or household electric wiring.
  • the silver-plated product can be used as the material of spring-loaded contact members for switches, as well as the material of switches of portable cellular phones and/or remote controllers of electrical apparatuses.
  • the silver-plated product can be also used as the material of charge terminals and high-pressure connectors of hybrid electric vehicles (HEVs) in which heavy-current flow and which have large heating values.
  • HEVs hybrid electric vehicles

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WO2021154771A1 (en) * 2020-01-28 2021-08-05 Materion Corporation Silver alloy clad structure for charging terminals and manufacturing method thereof

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EP3176798A1 (de) * 2015-12-04 2017-06-07 Abb Ag Kontaktsystem eines elektrischen installationsschalters
WO2021154771A1 (en) * 2020-01-28 2021-08-05 Materion Corporation Silver alloy clad structure for charging terminals and manufacturing method thereof

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CN104662208B (zh) 2019-01-25
US20150259815A1 (en) 2015-09-17
US9534307B2 (en) 2017-01-03
WO2014050772A1 (ja) 2014-04-03
EP2902533A4 (de) 2016-06-01
CN104662208A (zh) 2015-05-27
JP6193687B2 (ja) 2017-09-06
JP2014198895A (ja) 2014-10-23

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